DE2838608A1 - AZO REACTIVE DYES - Google Patents

Description

The present invention relates to azo reactive dyes of the formula

(I)

wherein

D = residue of a naphthalene mono-, di- or trisulfonic acid,

R = hydrogen, methyl, ethyl,

X = hydrogen, C [deep] 1-C [deep] 4-alkyl, C [deep] 1-C [deep] 4-alkoxy, halogen such as fluorine, chlorine or bromine, a carboxy, sulfo or acylamino group such as acetylamino , Ureido, formylamino, oxalylamino.

Examples of amines of the formula

D-NH [deep] 2 (II)

are the following:

2-amino-naphthalene-1-sulfonic acid,

2-amino-naphthalene-1,5-disulfonic acid,

2-amino-naphthalene-1,5,7-trisulfonic acid,

2-amino-naphthalene-3,6-disulfonic acid,

2-amino-naphthalene-3,6,8-trisulfonic acid,

2-amino-naphthalene-4,8-disulfonic acid,

2-amino-naphthalene-4,6,8-trisulfonic acid,

2-amino-naphthalene-5,7-disulfonic acid,

2-amino-naphthalene-6,8-disulfonic acid,

2-amino-naphthalene-6-sulfonic acid,

2-amino-naphthalene-8-sulfonic acid,

1-amino-naphthalene-4-sulfonic acid,

1-amino-naphthalene-5-sulfonic acid,

1-amino-naphthalene-6-sulfonic acid,

1-amino-naphthalene-7-sulfonic acid,

1-amino-naphthalene-4,6-disulfonic acid,

1-amino-naphthalene-4,7-disulfonic acid,

1-amino-naphthalene-3,6-disulfonic acid,

2-amino-6-nitro-naphthalene-4,8-disulfonic acid,

2-amino-6-acetylamino-naphthalene-4,8-disulfonic acid.

Preferred compounds correspond to the formulas

(III) wherein

R and X have the meaning given above and

R [deep] 1 = hydrogen or sulfo,

(IV)

wherein

R, R [deep] 1 and X have the meaning given above.

Particularly preferred are compounds of the formulas (III) and (IV) in which

a) X = hydrogen

b) X = sulfo

c) X and R = hydrogen

d) X = sulfo and

R = hydrogen.

The invention also relates to a process for the preparation of the compounds of the formula (I). It consists in using dyes of the formula

(V)

wherein D and R have the meaning given above condensed with 2,4,6-trifluoro-1,3,5-triazine with elimination of hydrofluoric acid and the resulting difluoro compound with an amine of the formula

(VI)

wherein

X has the meaning given above, converts to (I) with elimination of hydrofluoric acid.

The condensation of the dyes (V) with the s-trifluorotriazine is preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline pH.

The condensation is advantageously carried out in the pH range of 3-5. The released hydrogen fluoride is truncated by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The reaction of the difluoro compound with the amines (VI) is likewise preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline pH. The hydrogen fluoride released during the condensation is neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. Isolation of the difluoro compound is generally dispensed with.

In case that

X = sulfo or carboxy, the dyes (I) can also be prepared by first reacting p-sulfanilic acid or 4-carboxy-aniline with s-trifluorotriazine and then carrying out the condensation with the dye (V).

Another possibility for the preparation of (I) is that one diazotized amines (II) with coupling components of the formula

(VII) wherein

X and R have the meaning given above, combined in the weakly acidic, neutral to weakly alkaline range.

The dyes (V) are obtained by coupling the diazotized amines (II) with I-acid under conditions such that the coupling takes place preferably in the o-position to the hydroxyl group of the I-acid. However, coupling with an N-acylated I-acid is generally preferred, the acyl radical then being cleaved off by heating in an acidic or alkaline medium. Particularly suitable acyl radicals are acetyl, carbamoyl, methoxycarbonyl, ethoxycarbonyl or -CO- (I-acid urea by reaction with phosgene).

Examples of amines (VI) are as follows:

Aniline, 4-methyl-aniline, 4-ethyl-aniline, 4-iso-propyl-aniline, 4-methoxy-aniline, 4-ethoxy-aniline, 4-iso-propoxy-aniline, 4-fluoroaniline, 4-chloroaniline, 4-bromo-aniline, 4-carboxy-aniline, 4-sulfo-aniline, 4-acetylamino-aniline or 4-carbamoyl-aniline.

The new dyes are suitable for dyeing and printing materials containing hydroxyl or amide groups, such as textile fibers, threads and fabrics made from wool, silk, synthetic polyamide and polyurethane fibers and for dyeing and printing native or regenerated cellulose, with the treatment of cellulose materials expediently carried out in the presence of acid-binding agents and, if appropriate, by the action of heat according to the processes which have become known for reactive dyes.

The formulas given for the dyes are those of the corresponding free acids. The dyes were generally isolated in the form of the alkali salts, in particular the sodium salts, and used for dyeing.

example 1

55.3 g of the dye of the formula 1,5-disulfonaphthalene <2 azo 2> 1-hydroxy-3-sulfo-6-amino-naphthalene are dissolved in a mixture of 400 ml of water and 200 g of ice. 14 g of s-trifluorotriazine are then added dropwise and, at the same time, a pH of 3.5-4.5 is maintained by adding 20% strength soda solution. After the end of the acylation, 9.3 g of aniline are added, the pH is adjusted to 6 with 20% strength sodium carbonate solution and the mixture is stirred at pH 6 until the 2nd condensation has ended. Temp. 0-10 °.

The dye is deposited by adding sodium chloride, filtered off, dried and ground. The result is a light red powder that dissolves in water with an orange color. The dye conforms to the formula

Example 38

55.3 g of the dye of the formula 1,5-disulfo-napthalene <2 azo 2> 1-hydroxy-3-sulfo-6-aminonaphthalene are stirred in a mixture of 300 ml of water and 100 g of ice. An ice-cold aqueous solution of 28.8 g of 2,4-difluoro-6- (4'-sulfophenylamino) -1,3,5-triazine is then added and the condensation is carried out in the pH range from 5 to 6 and in the temperature range from 0 to 15 °. The dye is salted out, filtered off, dried and ground. The dye is identical to the product obtained according to Example 2).

Claims (9)

1) dyes of the formula wherein D = residue of a naphthalene mono-, di- or tri-sulfonic acid, R = hydrogen, methyl, ethyl, X = hydrogen, C [deep] 1-C [deep] 4-alkyl, C [deep] 1-C [deep] 4-alkoxy, halogen, such as fluorine, chlorine or bromine, a carboxy, sulfo or acylamino group. 2) dyes of the formula wherein R and X have the meaning given in claim 1) and R [deep] 1 = hydrogen or sulfo. 3) dyes of the formula wherein R and X in claim 1) and R [deep] 1 have the meaning given in claim 2). 4) dyes of claims 2) and 3), wherein X = hydrogen. 5) dyes of claims 2) and 3), wherein X = sulfo. 6) dyes of claims 2) and 3), wherein X and R = hydrogen. 7) dyes of claims 2) and 3), wherein X = sulfo and R = hydrogen. 8) Process for the preparation of the dyes of claim 1), characterized in that one dyes of the formula wherein D and R have the meaning given in claim 1), are reacted with 2,4,6-trifluoro-1,3,5-triazine with elimination of 1 mol of hydrofluoric acid and the resulting difluoro compound with amines of the formula wherein X has the meaning given in claim 1), condensed with elimination of 1 mol of hydrofluoric acid. 9) Use of the dyes of claims 1) to 7) for dyeing and printing hydroxyl-containing and amide-containing fiber materials.